EP0118095B1 - Procédé de fabrication d'esters alkyliques purs de l'acide 1-hydroxy-2-naphtoique - Google Patents

Procédé de fabrication d'esters alkyliques purs de l'acide 1-hydroxy-2-naphtoique Download PDF

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Publication number
EP0118095B1
EP0118095B1 EP84102057A EP84102057A EP0118095B1 EP 0118095 B1 EP0118095 B1 EP 0118095B1 EP 84102057 A EP84102057 A EP 84102057A EP 84102057 A EP84102057 A EP 84102057A EP 0118095 B1 EP0118095 B1 EP 0118095B1
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EP
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Prior art keywords
hydroxy
naphthoic acid
carbon atoms
radicals
atoms
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EP84102057A
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German (de)
English (en)
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EP0118095A2 (fr
EP0118095A3 (en
Inventor
Theodor Dr. Papenfuhs
Heinrich Dr. Volk
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
    • C07C65/105—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups polycyclic
    • C07C65/11—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups polycyclic with carboxyl groups on a condensed ring system containing two rings

Definitions

  • 1-Hydroxy-2-naphthoic acid alkyl esters are valuable intermediates for the production of dyes and, in particular, coloring layers in photographic materials, and they have aroused technical interest in the production of so-called “instant films” for the production of instant pictures and films.
  • Colorless, crystalline compounds of the formula are mainly used for the latter application in which R is a methyl, ethyl, n- or iso-propyl or n- or iso-butyl group, which is free from any impurities, in particular from synthesis-related impurities from the precursors, for example free from 1-hydroxy-naphthoic acid , 1-alkoxynaphthoic acid and 1-alkoxynaphthoic acid alkyl esters, and especially of higher molecular weight, resin-like compounds, such as those that arise in the technical production of 1-hydroxynaphthoic acid by carboxylation of 1-naphtholates with carbon dioxide according to Kolbe-Schmitt, and neither in the isolation process Hydroxynaphthoic acid, can still be removed quantitatively from its subsequent stages.
  • R is an alkyl radical of 8 to 20 carbon atoms
  • R 1 for an alkyl radical of 1 to 20 carbon atoms, for a hydroxyalkyl radical with 2 to 6 carbon atoms or for a phenylalkyl radical with 4 to 12 Carbon atoms in the alkyl radical
  • R 2 is an alkyl radical of 1 to 8 carbon atoms or a hydroxyalkyl radical of 2 to 6 carbon atoms
  • R 3 represents an alkyl radical of 1 to 8 carbon atoms or the benzyl radical.
  • Quaternary ammonium compounds of the general formula (II) which can be used according to the invention are, for example, the following:
  • aqueous solutions of pure mono-alkali metal salts of 1-hydroxy-2-naphthoic acid obtained in the course of the process according to the invention can be used for the separation of impurity-free 1-hydroxy-2-naphthoic acid by adding mineral acids, the separated, neutral-washed and dried 1-hydroxy -2-naphthoic acid can be redissolved in sodium hydroxide solution and esterified with dialkyl sulfate according to the process.
  • the aqueous solution is preferably used directly, as a result of which the additional isolation step is omitted and a possible deterioration in quality (for example by washing with technical water, possibly storage and / or drying) is avoided.
  • the esterification is expediently carried out in such a way that the aqueous mono-alkali metal salt solution of 1-hydroxy-2-naphthoic acid freed from resins according to the invention at 30 ° -80 ° C., preferably 40 ° to 60 ° C.
  • Suitable dialkyl sulfates are preferably technically easily accessible compounds, such as dimethyl sulfate and diethyl sulfate.
  • the water-moist or dried alkyl 1-hydroxy-2-naphthoate obtained according to the invention can be used to improve the aspect (crystallinity) and / or to further improve quality (removal of any free 1-hydroxy-2-naphthoic acid contained) from alkanols, preferably that of the alkyl ester group in each case Use product corresponding alkanol, recrystallized.
  • 1-hydroxy-2-naphthoic acid alkyl esters prepared in this way (in addition to the resins contained in the starting product, which can only be removed by the process according to the invention) still contain unreacted 1-hydroxy-2-naphthoic acid, of which, however, they are recrystallized once from alkanols, expediently can be freed from the alkanol corresponding to the ester group in order to exclude the risk of transesterification.
  • the cationic, surface-active compounds of general formulas 11 and 111 used according to the invention surprisingly produce quantitative, water-insoluble precipitates with the resins contained in the preparation of 1-hydroxy-2-naphthoic acid, which, depending on the chosen precipitating temperatures and the constitution of the surface-active compound, in solid or liquid form, nothing being known about the nature of the precipitation of the resins.
  • the mixture is heated to about 60 ° C. with stirring, 1.8 parts of coconut-benzyl-dimethylammonium chloride are added and the mixture is stirred at 60 ° C. for 5 minutes.
  • the precipitated black-brown precipitate is filtered off and 277 parts of dimethyl sulfate are added to the clear, light-colored filtrate at 55-60 ° C. in 3 hours.
  • the pH value is kept constant at 5.5 by simultaneous addition of 200 parts of 33% sodium hydroxide solution.
  • the mixture is subsequently stirred for 30 minutes, 100 parts of water and 22 parts of 25% strength aqueous ammonia are added in succession, the mixture is stirred at 55-60 ° C. for a further hour and then cooled to 20 ° C.
  • the colorless crystalline product produced in this way contains no impurities apart from small amounts of 1-hydroxy-2-naphthoic acid (0.1-0.2%). By simply recrystallizing from 5-6 times the amount of methanol, these can also be removed quantitatively (melting point then 76.5-77 ° C).
  • trioctyl-methylammonium chloride 4.0 parts are added to the dark brown solution. After 10 minutes, 5 parts of activated carbon and 5 parts of a mineral filter aid are also added, the mixture is stirred for another 5 minutes and filtered through a preheated suction filter. The colorless, clear filtrate is cooled to 40 ° C. 252 parts of dimethyl sulfate are added dropwise uniformly in the course of one hour, the pH being kept constant at 6.0 by simultaneous addition of 120 parts of 33% strength sodium hydroxide solution.
  • the methyl 1-hydroxy-2-naphthoate precipitates in the form of colorless crystals.
  • the mixture is stirred for 3 hours, adjusted to pH 10.0 by adding 6 parts of 33% sodium hydroxide solution, stirred for a further hour and then cooled to 20 ° C. It is then suctioned off, washed neutral with water and dried. 191 parts of 1-hydroxy-2-naphthoic acid methyl ester of melting point 76-77 ° C. are obtained, which contains no detectable impurities. (Pure content determined by potentiometric titration: 99.9-100%; yield: 94.6% of theory, based on 1-hydroxy-2-naphthoic acid). If you use appropriate amounts of potassium hydroxide instead of the sodium hydroxide solution and otherwise work in the manner specified, you will get an identical result.
  • the ethyl 1-hydroxy-2-naphthoate escapes in the form of colorless, coarse crystals.
  • the mixture is stirred at 35 ° C for 1 hour, the excess diethyl sulfate is destroyed by adding 3 parts of 33% sodium hydroxide solution, cooled to 10 ° C and the crystals are isolated by filtration.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (2)

1. Procédé de préparation d'esters alkyliques purs de l'acide 1-hydroxy-2-naphtoïque de formule générale 1 ci-dessous:
Figure imgb0014
dans laquelle R désigne un alkyle en Ci-C5 à chaîne linéaire ou ramifiée, procédé caractérisé en ce que l'on règle à un pH de 5,5 à 6,5, avec un acide minéral, une solution aqueuse des sels mono- et/ou di-alcalines de l'acide 1-hydroxy-2-naphtoïque obtenue par carboxylation d'un 1-naphtolate de métal alcalin (suivant Kolbe-Schmitt) suivie d'un traitement à l'eau, ou par dissolution dans une lessive alcaline aqueuse d'un acide 1-hydroxy-2-naphtoïque formé de cette manière mais qui a été isolé, puis on ajoute un composé surfactif cationique soit:
(1) de formule générale Il:
Figure imgb0015
dans laquelle R, R1, R2 et R3 représentent des radicaux aliphatiques en Ci à C30 identiques ou différents, à chaîne linéaire ou ramifiée, saturés ou avec une, deux trois doubles liaisons carbone- carbone, pouvant avoir de 1 à 3 hétéroatomes ou groupes tels que -0-, -S-, -NH-,
Figure imgb0016
ou des atomes d'azote quaternisés, et/ou des groupes amide carboxylique, ainsi qu'aux extrémités des chaînes des substituants ionogènes, ou bien des radicaux hydroaromatiques carbocycy- cliques ou cycloaliphatiques ayant de 4 à 8 atomes de carbone dans le cycle, radicaux cycliques qui peuvent porter des chaînes latérales aliphatiques en Ci à C12 ou des atomes d'halogènes, par exemple de chlore ou de brome, ou des radicaux aral- kyles dont l'alkyle a de 1 à 30 atomes de carbone, de préférence de 1 à 12, et l'aryle est un groupe phényle ou naphtyle dont le cycle peut avoir comme substituants des hydroxyles, des groupes alkyles ou alcoxy inférieures et/ou des atomes d'halogènes, ou encore des radicaux aryles, dont le cycle peut avoir comme substituants des hydroxyles, des alkyles ou des alcoxy inférieurs, des groupes carboxamides ou sulfonamides ou des atomes d'halogènes, par exemple de chlore, la somme des atomes de carbone de R, R1, R2 et R3 étant au moins égale à 8 et 2 ou 3 des radicaux aliphatiques R, R1, R2 et R3 situés sur un atome d'azote quaternaire pouvant former avec l'atome d'azote un hétérocycle éventuellement avec des doubles liaisons, sur lequel peut être condensé un noyau benzénique, et X(-) représente l'équivalent d'un acide minéral ou organique, soit
(2) de formule générale III:
Figure imgb0017
dans laquelle les symboles R, Ri, R2, R3 et X(-) ont les mêmes significations que dans la formule Il ci-dessus, la somme des atomes de carbone de R, Ri, R2 et R3 étant au moins égale à 8 et 2 ou 3 des radicaux aliphatiques R, Ri, R2 et R3 peuvent former avec l'atome de phosphore un hétérocycle avec éventuellement des doubles liaisons, l'un ou l'autre de ces composés dans une proportion de 0,5 à 5% du poids de l'acide 1-hydroxy-2-naphtoï- que se trouvant dans la solution, on élimine ou on sépare par filtration les précipités qui se sont formés à l'état solide ou liquide à partir des résines en une réaction quantitative, à des températures de 50 à 100°C, éventuellement après avoir ajouté des adsorbants et/ou des adjuvants de filtration, et on estérifie avec un sulfate de dialkyle le sel de métal monoalcalin pur de l'acide 1-hydroxy-2-naphtoïque qui se trouve dans la solution aqueuse à un pH de 5,5 à 6,5, à des températures de 30 à 80 °C.
2. Procédé selon la revendication 1 caractérisé en ce que, après avoir séparé les précipités formés à partir des résines présentes, avant d'effectuer l'estérification avec le sulfate de dialkyle, on fait précipiter à l'état d'acide 1-hydroxy-2-naph- toïque le sel monoalcalin pur de cet acide obtenu en solution aqueuse en ajoutant un acide minéral, on lave cet acide 1-hydroxy-2-naphtoïque jusqu'à neutralité, on le sèche et on le redissout dans une lessive de soude.
EP84102057A 1983-03-04 1984-02-28 Procédé de fabrication d'esters alkyliques purs de l'acide 1-hydroxy-2-naphtoique Expired EP0118095B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3307637 1983-03-04
DE19833307637 DE3307637A1 (de) 1983-03-04 1983-03-04 Verfahren zur herstellung von reinen 1-hydroxy-2-naphtoesaeurealkylestern

Publications (3)

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EP0118095A2 EP0118095A2 (fr) 1984-09-12
EP0118095A3 EP0118095A3 (en) 1986-02-19
EP0118095B1 true EP0118095B1 (fr) 1988-03-30

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US (1) US4521617A (fr)
EP (1) EP0118095B1 (fr)
JP (1) JPS59167544A (fr)
DE (2) DE3307637A1 (fr)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3468942A (en) * 1966-10-05 1969-09-23 Tenneco Chem Method for the recovery of hydroxy aromatic carboxylic acids
DE2407187B2 (de) * 1974-02-15 1976-01-08 Hoechst Ag, 6000 Frankfurt Verfahren zur Herstellung von aromatischen Hydroxycarbonsäurealkylestern
NL7506445A (nl) * 1974-06-04 1975-12-08 Hoechst Ag Werkwijze voor het winnen van 2-hydroxynaftaleen- carbonzuren uit reactiemengsels van alkalizouten van 2-hydroxynaftaleen met kooldioxyde.
DE2911667A1 (de) * 1979-03-24 1980-10-02 Hoechst Ag Verfahren zur gewinnung von 2-hydroxynaphthalin-3-carbonsaeure aus den umsetzungsgemischen der alkalisalze des 2-hydroxynaphthalins mit kohlendioxid
DE3224148A1 (de) * 1982-06-29 1983-12-29 Hoechst Ag, 6230 Frankfurt Quartaere ammoniumsalze und deren verwendung als stroemungsbeschleuniger

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EP0118095A2 (fr) 1984-09-12
EP0118095A3 (en) 1986-02-19
US4521617A (en) 1985-06-04
DE3470158D1 (en) 1988-05-05
DE3307637A1 (de) 1984-09-06
JPS59167544A (ja) 1984-09-21

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